PHOSPHORIC ACID ESTERS, METHOD OF SYNTHETIZING THEM AND USE THEREOF AS DISPERSANTS

Abstract

The invention concerns a phosphoric acid ester of Formula (I) or (II), wherein: A, B and R represents an aliphatic, cycloaliphatic and/ or aromatic moiety; Q represents CH.sub.2, O or COO; n+m is inferior to 3; and X+Y is less than 7, and wherein the phosphoric acid ester has an average molecular weight M.sub.n of 70 to 10,000 g/mol. The invention also concern the process for making the phosphoric acid ester of Formula (I) or (II), and there us as dispersants of particles in a liquid medium, such as water, solvent, plasticizer or resin. Advantageously, the process allows the preparation of new high performing polymeric phosphate esters with less acidic character that are majorly a phosphate diester. Also, a 100% active liquid solvent free polyester phosphate ester can be effectively prepared.

##STR00001##

Claims

1. A phosphoric acid ester of Formula (I) or (II) as follows: ##STR00010## wherein: A, B and R represents an aliphatic, cycloaliphatic and/or aromatic moiety; Q represents CH.sub.2, O or COO; n+m is inferior to 3; and X+Y is less than 7, and wherein the phosphoric acid ester has an average molecular weight M.sub.n of 70 to 10,000 g/mol.

2. The phosphoric acid ester as claimed in claim 1, wherein in said phosphoric acid ester, R represents an alkyl or aryl group or an aliphatic alcohol/carboxylic acid, aromatic alcohol/carboxylic acid, aliphatic alcohol alkoxylate, aliphatic alcohol alkoxylate carboxylic acid, aromatic alcohol alkoxylate, aromatic alcohol alkoxylate carboxylic acid, alkyl-aryl alkoxylate, alkyl-aryl alkoxylate carboxylic acid, aryl alkoxylate or aryl alkoxyate carboxylic acid.

3. The phosphoric acid ester as claimed in claim 1, wherein in said phosphoric acid ester, A and B are the same or different, and represent each an alkyl or aryl group, an alkoxylated alcohol group, an alkyl aryl alkoxylate or aryl alkoxylate group.

4. The phosphoric acid ester as claimed in claim 3, wherein A and/or B are modified with a carboxylic ester functional group or an urethane functional group.

5. The phosphoric acid ester as claimed in claim 4, wherein such carboxylic ester functional group is from a polycaprolactone.

6. The phosphoric acid ester as claimed in claim 5, wherein the polycaprolactone is an alcohol ethoxylate modified polycaprolactone.

7. A process for the making of the phosphoric acid ester as claimed in claim 1, comprising the step of: reacting an alkyl or aryl epoxide or mono/poly glycidyl ether/ester of formula (III): ##STR00011## wherein R and Q are as defined in claim 1, and G is an integer from 1 to 7; with: a mono- or diphosphate ester of formula (IV), (V), (VI) or (VII): ##STR00012## wherein A and B are as defined in claim 1.

8. The process as claimed in claim 7, wherein the mono- or diphosphate ester of Formula (IV), (V), (VI), or (VII) is a reaction product of A or B with polyphosphoric acid or phosphorous pentoxide.

9. The process as claimed in claim 7, wherein in said phosphoric acid ester, R represents an alkyl or aryl group or an aliphatic alcohol/carboxylic acid, aromatic alcohol/carboxylic acid, aliphatic alcohol alkoxylate, aliphatic alcohol alkoxylate carboxylic acid, aromatic alcohol alkoxylate, aromatic alcohol alkoxylate carboxylic acid, alkyl-aryl alkoxylate, alkyl-aryl alkoxylate carboxylic acid, aryl alkoxylate or aryl alkoxyate carboxylic acid.

10. The process as claimed in claim 7, wherein in said phosphoric acid ester, A and B are the same or different, and represent each an alkyl or aryl group, an alkoxylated alcohol group, an alkyl aryl alkoxylate or aryl alkoxylate group.

11. The process as claimed in claim 10, wherein A and/or B are modified with a carboxylic ester functional group or an urethane functional group.

12. The process as claimed in claim 11, wherein such carboxylic ester functional group is from a polycaprolactone.

13. The process as claimed in claim 12, wherein the polycaprolactone is an alcohol ethoxylate modified polycaprolactone.

14. A method for wetting and/or dispersing particles in a liquid medium, the method comprising: incorporating an amount of the phosphoric acid ester as claimed in claim 1 or obtained by the process of claim 7, in the liquid medium, the liquid medium comprising said particles or the particles being added to the liquid medium after said amount of the phosphoric acid ester.

15. The method as claimed in claim 14, wherein the phosphoric acid ester is used in its acidic form or is neutralized with an alkali metal, ammonia or an organic amine.

16. The method as claimed in claim 15, wherein said alkali metal is sodium or potassium.

17. The method as claimed in claim 15, wherein the organic amine is monoalkyl, dilalkyl, trialkyl, monoalkanol. dialkanol. trialkanol amine derivative, fatty imidazoline derivatives, polyalkylenepolaymine or polalkyleneimine derivatives.

18. The method as claimed in claim 17, wherein the organic amine is trialkyl amines, tall oil fatty imidazoline or acrylate modified polyethyleneimines.

19. The method as claimed in claim 14, wherein said particles comprises pigments, fillers or extenders in paint or coatings, composites, plastics, ink medium or mixture thereof.

20. The method as claimed claim 14, wherein the liquid medium comprises one or more of water, solvent, plasticizer or resin.

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0036] Novel phosphoric acid esters and their salts will be described hereinafter. Although the invention is described in terms of specific illustrative embodiments, it is to be understood that the embodiments described herein are by way of example only and that the scope of the invention is not intended to be limited thereby.

[0037] The terminology used herein is in accordance with definitions set out below.

[0038] As used herein % or wt. % means weight % unless otherwise indicated. When used herein % refers to weight % as compared to the total weight percent of the phase or composition that is being discussed.

[0039] By about, it is meant that the value of weight %, time, temperature or the like can vary within a certain range depending on the margin of error of the method or device used to evaluate such weight %, time, or temperature. A margin of error of 10% is generally accepted.

[0040] According to a preferred embodiment, it is disclosed a phosphoric acid ester of Formula (I) or as follows:

##STR00005##

wherein: A, B and R represents an aliphatic, cycloaliphatic and/or aromatic moiety; Q represents CH.sub.2, O or COO; n+m is inferior to 3; and X+Y is less than 7, and wherein the phosphoric acid ester has an average molecular weight M.sub.n of 70 to 10,000 g/mol.

[0041] According to a preferred embodiment, R represents an alkyl or aryl group or an aliphatic alcohol/carboxylic acid, aromatic alcohol/carboxylic acid, aliphatic alcohol alkoxylate, aliphatic alcohol alkoxylate carboxylic acid, aromatic alcohol alkoxylate, aromatic alcohol alkoxylate carboxylic acid, alkyl-aryl alkoxylate, alkyl-aryl alkoxylate carboxylic acid, aryl alkoxylate or aryl alkoxyate carboxylic acid.

[0042] According to a preferred embodiment, A and B are the same or different, and represent each an alkyl or aryl group, an alkoxylated alcohol group, an alkyl aryl alkoxylate or aryl alkoxylate group. Preferably, A and/or B are modified with a carboxylic ester functional group or an urethane functional group.

[0043] According to a preferred embodiment, the carboxylic ester functional group is from a polycaprolactone. More preferably, the polycaprolactone is an alcohol ethoxylate modified polycaprolactone.

[0044] According to another aspect, it is disclosed a process for the making of a phosphoric acid ester of Formula (I) or (II) as follows:

##STR00006##

wherein: A, B and R represents an aliphatic, cycloaliphatic and/or aromatic moiety; Q represents CH.sub.2, O or COO; n+m is inferior to 3; and X+Y is less than 7, and wherein the phosphoric acid ester has an average molecular weight M.sub.n of 70 to 10,000 g/mol, the process comprising the step of: [0045] reacting an alkyl or aryl epoxide or mono/poly glycidyl ether/ester of formula (III):

##STR00007## [0046] wherein R and Q are as defined herein above, and G is an integer from 1 to 7; with: [0047] a mono- or diphosphate ester of formula (IV), (V), (VI) or (VII):

##STR00008##

wherein A and B are as defined above.

[0048] According to a preferred embodiment, the mono- or diphosphate ester of Formula (IV), (V), (VI), or (VII) is a reaction product of A or B with polyphosphoric acid or phosphorous pentoxide.

[0049] According to another aspect, it is disclosed a method for wetting and/or dispersing particles in a liquid medium, the method comprising: [0050] incorporating an amount of a phosphoric acid ester of Formula (I) or (II) as follows:

##STR00009##

wherein: A, B and R represents an aliphatic, cycloaliphatic and/or aromatic moiety; Q represents CH.sub.2, O or COO; n+m is inferior to 3; and X+Y is less than 7, and [0051] wherein the phosphoric acid ester has an average molecular weight M.sub.n of 70 to 10,000 g/mol; [0052] in the liquid medium, the liquid medium comprising said particles or the particles being added to the liquid medium after said amount of the phosphoric acid ester.

[0053] In other embodiments, the phosphoric acid esters of Formula (I) and (II) as defined herein and salts thereof, can be used for wetting and/or dispersing particles in a liquid medium.

[0054] According to a preferred embodiment, the phosphoric acid ester is used in its acidic form or is neutralized with an alkali metal, ammonia or an organic amine. More preferably, the alkali metal is sodium or potassium, and the organic amine is monoalkyl, dilalkyl, trialkyl, monoalkanol. dialkanol. trialkanol amine derivative, fatty imidazoline derivatives, polyalkylenepolaymine or polalkyleneimine derivatives. More preferably, the organic amine is trialkyl amines, tall oil fatty imidazoline or acrylate modified polyethyleneimines.

[0055] According to a preferred embodiment, the particles comprises pigments, fillers or extenders in paint or coatings, composites, plastics, ink medium or mixture thereof.

[0056] According to a preferred embodiment, the liquid medium comprises one or more of water, solvent, plasticizer or resin.

EXAMPLES

[0057] The term parts herein means parts by weight or can also be expressed in grams.

Intermediate 1 (1 Mole MPEG 350 with 5 Mole Caprolactone)

[0058] Under a protective nitrogen atmosphere, 38 parts of a methoxypolyethyleneglycol (MPEG) having an average molecular weight of 350 were combined with 62 parts caprolactone and 0.4 parts p-toluene sulfonic acid and heated to 160? C. The mixture was stirred at this temperature until a solid content of at least 98% was reached. The resulting polyether-polyester has an average molecular weight of 800.

Intermediate 2 (1 Mole MPEG 350 with 4 Moles Caprolactone)

[0059] The procedure was the same as described in Intermediate 1, except that instead of 5 mole of caprolactone, 4 mole of caprolactone (49.6 parts) was used with addition of 0.4 parts p-toluene sulfonic acid and heated to 160? C. The mixture was stirred at this temperature until a solid content of 98% or more was reached.

Intermediate 3 (I Mole MPEG 350 with 3 Mole Caprolactone and 1 Mole Valerolactone)

[0060] The procedure was the same as Intermediate 1 except that 44.16 parts of MPEG having an average molecular weight of 350 were heated with 43.20 parts of caprolactone and 12.63 parts of ?-valerolactone and heated to a temperature of 160? C. Then 0.2 parts of dibutyl tin dilaurate were added. The mixture was stirred at this temperature until a solid content of 98% or more was reached.

Intermediate 4 (Polyethyleneimine (PEI) Reaction Product with with 2-ethylhexyl Acrylate)

[0061] In a four-necked flask with agitator, thermometer, reflux cooler and nitrogen inlet tube, 30 gm of epomine SP-018 are placed and heated to 80? C. with agitation under N2 gas. Then 70 gm of 2-ethyl hexyl acrylate added over period two hours, after complete addition, stirring was continued for additional 8 hours.

Intermediate 5 (Tall Oil Fatty Acid Reaction Product with Hydroxyethyl Ethylene Diamine)

[0062] In a four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet line, 1 mole of TOFA (100 parts) were added to 1 mole of the hydroxylethyl ethylene diamine (35.86 parts) and stirred for 3 hours at about 140? C. followed by heating under vacuum at 220? C. for 5 hours. The hydroxide compound was obtained.

General Synthesis Procedure for Phosphate Ester

[0063] In a four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet line, Y g of thermal 116 polyphosphoric acid were added to X g (1 mole) of the monohydroxy compound and stirred while excluding moisture. After 5 hours of stirring at about 80? C., a phosphoric acid monoester was obtained. Then Z g of epoxide compound were added at exactly 80? C. and stirred at this temperature for 6 hrs. Methoxy propyl acetate and or C9-C10 aromatic solvent may optionally be used for dilution during or after the reaction. X, Y and Z are provided in the following Table 1 below.

TABLE-US-00001 TABLE 1 Y (g) of Epoxide Z (g) of Exam- Hydroxy Polyphos- containing epoxide ple compound X (g) phoric 116 compound compound P1 Intermediate 1 100 9.17 C12-C14 84.28 glycidyl ether P2 Intermediate 2 87.6 9.16 C12-C14 84.28 glycidyl ether P3 Intermediate 3 100 10.16 Ethyl hexyl 53.22 glycidyl ether P4 MPEG 350 100 24.14 Ethyl hexyl 53.22 glycidyl ether P5 Intermediate 1 100 9.17 Ethylhexyl 20.22 glycidyl ether P6 Lutensol ON 100 17.97 Phenyl glycidyl 31.9 70 ether P7 Butyl EO PO 100 8.45 Ethyl hexyl 18.63 glycidyl ether P8 Lutensol TO7 100 16.9 Allyl glycidyl 22.9 ether P9 Ethylhexanol 100 14.81 Phenyl glycidyl 26.32 10 ethoxylate ether P10 Lutensol ON 100 17.97 Styrene oxide 25.56 70 P11 Butyl EO PO 100 8.45 Ethyl 18.63 hexylglycidyl ether P12 Intermediate 1 100 9.17 Butane diol 21.97 diglycidylether

[0064] Butyl EO PO: Butanol ethoxylated propoxylated with and ethylene oxide to propylene oxide molar ratio of 1:1 with an average molecular weight of 1000

[0065] Lutensol ON 70: an isodecyl alcohol 7 ethoxylate from BASF

[0066] Lutensol TO 7: an isotridecyl alcohol 7 ethoxylate from BASF

[0067] Examples P13-P16 in Table 2 below were prepared as a neutralized derivative of some of selected Examples P1-P12 of Table 1 above. Neutralizing agents can be potassium hydroxide, sodium hydroxide, ammonium hydroxide solutions or any amine containing compounds like the previously prepared Intermediate 4 and 5. Neutralization can be carried out in presence or absence of a solvent.

TABLE-US-00002 TABLE 2 Phos- Phosphate Neutral- phate ester izing Ex- ester derivative Solvent agent am- deriv- quantity quantity Neutralizing quantity ples ative (parts) Solvent (parts) agent (parts) P13 P3 50 Intermediate 7.99 4 P14 P4 50 Intermediate 28.67 5 P15 P6 50 Water 40 Sodium 10 hydroxide (50%) P16 P11 50 Water 37.5 Sodium 12.5 hydroxide (50%)

Example 1

[0068] Dispersing agents of examples P5, P6 and P9 were diluted with a mixture of 2-methoxy propyl acetate and Aromatic 100 solvent mixture of 1:1 ratio to an active ingredient of 52%. They were then evaluated in titanium dioxide dispersion in 2K-PU coating system against DELTA-DC 3080 (a commercial wetting and dispersing agent supplied by DELTA specialties) as mentioned in Table 3 below.

TABLE-US-00003 TABLE 3 Component Quantity (parts or grams) Macrynal VSM 2706/60X 36 Dispersing agent 3.6 Titanium dioxide (Dupont-R902) 94.5 Methoxy propyl acetate and Aromatic 100 15.9 1:1 mixture

[0069] Macrynal VSM 2706/60X: a hydroxy functional acrylic resin supplied by Allnex company.

[0070] Aromatic 100: C9 aromatic fluid supplied by ExxonMobil company.

[0071] Grinding was carried hour for 1 hour in a Skandex shaker using glass beads as a grinding media. The prepared pigment concentrate is then mixed with the equivalent amount of a polymeric aliphatic isocyanate and directly applied as a drawdown films. Table 4 below summarizes the results.

TABLE-US-00004 TABLE 4 DELTA-DC 3080 P5 P6 P9 Viscosity in 2850 2860 3490 2960 mPa .Math. s at rpm 60 and spindle 4 using brookfield viscometer Gloss @ 60 83 88 91 83.6 Color parameters L 95.8 95.89 96.02 96.06 a ?1.3 ?1.34 ?1.33 ?1.29 b ?0.47 ?0.65 ?0.56 ?0.50 Hiding power.sup.2 2 2 1 1

[0072] L, a and b are color parameters according to the Lab color scale.

[0073] Hiding power is a score from 1 to 4. 1 is the highest hiding and 4 is the lowest.

Example 2

[0074] Dispersing agents of examples P5 and P10 were diluted with a mixture of 2-methoxy propyl acetate and Aromatic 100 solvent mixture of 1:1 ratio to an active ingredient of 52%. They were then evaluated in titanium dioxide dispersion in saturated polyester/melamine formaldehyde coating system against DELTA-DC 3080 (a commercial wetting and dispersing agent supplied by DELTA specialties) as mentioned below in Table 5.

TABLE-US-00005 TABLE 5 Component Quantity (parts or grams) Synolac 5070S-65 36 Dispersing agent 3.6 Titanium dioxide (Dupont-R902) 94.5 Aromatic 100 8.9

[0075] Synolac 5070S-65 is a saturated polyester resin supplied by Arkema company

[0076] Grinding was carried hour for 1 hour in a Skandex shaker using glass beads as a grinding media. The prepared pigment pastes is then converted into a final white paint and mixed with equivalent amount of n-butylated high imino melamine crosslinker (SETAMINE? US-138 BB-70) and directly applied on a drawdown films and cured. Table 6 below summarizes the results for both the pigment paste and the final paint.

TABLE-US-00006 TABLE 6 DELTA-DC 3080 P5 P10 Viscosity in mPa .Math. s at rpm 7560 5530 8020 60 and spindle 4 using brookfield viscometer Gloss @ 60 98 110 102 Color parameters L 96.6 96.58 97.09 a ?1.29 ?1.28 ?1.25 b 0.1 0.16 0.1 Hiding power 2 2 1

Example 3

[0077] Dispersing agents of examples P1, P5, P7 and P10 were diluted with a mixture of 2-methoxy propyl acetate and Aromatic 100 solvent mixture of 1:1 ratio to an active ingredient of 52%. They were then evaluated in titanium dioxide dispersion in a highly filled solvent free epoxy system against DELTA-DC 3080 (a commercial wetting and dispersing agent supplied by DELTA specialties) as mentioned below in Table 7.

TABLE-US-00007 TABLE 7 Component Quantity (parts or grams) Epotec YD-128 50 Dispersing agent 2 Titanium dioxide (Dupont R902) 10 Calcium carbonate 130 Benzyl alcohol 8

[0078] Epotec YD-128 is a solvent free unmodified Bisphenol-A based Liquid Epoxy Resin supplied by Aditya Birla company

[0079] Dispersion was carried out by 1 hour in a Skandex shaker using glass beads as a grinding media The prepared paint is then evaluated for viscosity and flowability. Table 8 below summarizes the results:

TABLE-US-00008 TABLE 8 DELTA- DC 3080 P1 P5 P7 P10 Viscosity in Very high 58290 53990 56390 57090 mPa .Math. s at viscosity rpm 6 and spindle 4 using brookfield viscometer Flowability Non- flowable flowable flowable Flowable flowable

Example 4

[0080] Dispersing agents of examples P1, P4 and P5 were diluted with a mixture of 2-methoxy propyl acetate and Aromatic 100 solvent mixture of 1:1 ratio to an active ingredient of 52%. They were then evaluated in titanium dioxide dispersion in saturated polyester/cellulose acetate butyrate (CAB) white system against DELTA-DC 3080 (a commercial wetting and dispersing agent supplied by DELTA specialties) as mentioned in Table 9 below.

TABLE-US-00009 TABLE 9 Component Quantity (parts or grams) Synolac 5070S-65 12 Dispersing agent 1.2 Titanium dioxide (Dupont R902) 31.5 Methoxy propyl acetate and Butyl acetate 5.3 1:1 mixture

[0081] Grinding was carried hour for 1.5 hour in a Skandex shaker using glass beads as a grinding media The prepared pigment pastes is then mixed 1:1 with the below CAB prepared solution according to Table 10.

TABLE-US-00010 TABLE 10 Component Quantity (parts or grams) CAB 381-2 8 Xylene 32 Methoxy propyl acetate:Butyl acetate 1:1 60 mixture

[0082] CAB 381-2 is a cellulose ester with high butyryl content supplied by Eastman company

[0083] Drawdown films of the prepared paint is subject to curing, followed by application of a clear 2K-PU film and then being evaluated. The results are summarized in Table 11.

TABLE-US-00011 TABLE 11 DELTA-DC 3080 P1 P4 P5 Viscosity in mPa .Math. s at rpm 1600 1650 1620 1550 60 and spindle 4 using brookfield viscometer Color parameters L 95.4 95.36 95.61 95.38 a ?0.7 ?0.67 ?0.70 ?0.71 b 0.1 ?0.18 ?0.13 ?0.10 Hiding power 3 2 1 1

Example 5

[0084] Dispersing agent of example P14 were diluted with a mixture of 2-methoxy propyl acetate and Aromatic 100 solvent mixture of 1:1 ratio to an active ingredient of 52%. It was then evaluated in unsaturated polyester car putty system against a commercial product Disperbyk 969 as mentioned in Table 12.

TABLE-US-00012 TABLE 12 Component Quantity (part or grams) USP-EAGLE (BF36/62)62% 32 Dispersing agent 1 Styrene monomer 3 Titanium dioxide 3 Barium sulfate 15.6 Talc 37 Calcium carbonate 7 Aerosil 200 0.25 Thixcin R 0.5

[0085] USP-EAGLE (BF36/62)62%: a unsaturated polyester resin supplied by Eagle chemicals

[0086] Dispersion was carried out for 30 minutes using a high speed disperser at 800 rpm. The prepared putty is then incubated for 1 month at 60? C. and tested for syneresis and settling. The comparison between P14 and the commercial product Disperbyk 969 is made according to Table 13.

TABLE-US-00013 TABLE 13 Commercial product P14 Viscosity in mPa .Math. s at rpm 1 and 93600 88000 spindle 4 using brookfield viscometer 24 hours after preparation Syneresis 3 1 Settling.sup.2 2 1

[0087] Syneresis is a score of 1 to 4 is given. 1 means little or no syneresis and 4 means strong syneresis.

[0088] Settling is a score of 1 to 4 is given. 1 means little or no settling and 4 means strong settling.

Example 6

[0089] Dispersing agent of example P15 was evaluated in dispersions of inorganic pigments in a water-based pigment paste against DELTA-DC 4073 (a commercial wetting and dispersing agent supplied by DELTA specialties) as mentioned in Table 14 below.

TABLE-US-00014 TABLE 14 Quantity Quantity (part or gram) - (part or gram) Component Dispersion I Dispersion II Bayferrox 3920 (PY42) 60 Bayferrox 130M (PR101) 65 Water 30.4 25.4 DELTA-FC 1590 0.6 0.6 Dispersing agent 9 9

[0090] Bayferrox 3920: a yellow iron oxide pigment supplied by Lanxess

[0091] Bayferrox 130M: a red iron oxide pigment supplied by Lanxess

[0092] DELTA-FC 1590: a silicone based emulsion defoamer supplied by DELTA specialties

[0093] Grinding was carried hour for 1.5 hour in a Skandex shaker using glass beads as a grinding media The prepared colorants are then used to tint a ready matt water based emulsion paint. The results for the prepared pastes and the tinted system are then evaluated as below in Table 15.

TABLE-US-00015 TABLE 15 DELTA-4073 P15 DELTA-4073 P15 (PY42) (PY42) (PR101) (PR101) Viscosity in 2290 2180 2510 2300 mPa .Math. s at rpm 60 and spindle 4 using brookfield viscometer Tinting L HHH L H strength

[0094] Tinting strength: a relative evaluation is given to compare the samples. H means higher, L means lower and E means equal tinting strength.

Example 7

[0095] Dispersing agent of example P13 was evaluated in solvent free epoxy mid-grey color coating against DELTA-S 5206 (a commercial wetting and dispersing agent from DELTA specialties) with following spec according to Table 16.

TABLE-US-00016 TABLE 16 Component Quantity (part or gram) Epotec YD-128 37.4 Lapox ARD-13 6 Dispersing agent 0.85 DELTA-FC 1722 0.7 Thixgel 34 0.5 Titanium dioxide (Dupont R902) 10 Bayferrox 3920 (PY42) 0.43 MONARCH 570 0.4 Barium sulfate 18 Calcium Carbonate 22.9 Benzyl alcohol 1.8 DELTA-SC 2780 1.0

[0096] Lapox ARD-13: a low viscosity, long chain aliphatic mono epoxide reactive diluent based on C12-C14 alcohol supplied by Atul company

[0097] Thixgel 34: an organoclay rheological additive supplied by Zhejiang Auto Full Clay Chemical Co. Ltd.

[0098] DELTA-FC 1722: a silicone containing defoamer supplied by DELTA specialties.

[0099] MONARCH 570: a high structure carbon black pigment supplied by Cabot corp.

[0100] DELTA-SC 2780: an acrylate based flow and leveling agent supplied by DELTA specialties

[0101] Grinding was carried hour for 1 hour in a Skandex shaker using glass beads as a grinding media. The prepared paint is then mixed with the equivalent amount of a commercially available polyamide hardener for curing. Drawdown films are applied and then being evaluated. The results are summarized in Table 17.

TABLE-US-00017 TABLE 17 DELTA-S 5206 P14 Viscosity in mPa .Math. s at rpm 60 and spindle 4 using 8200 5200 brookfield viscometer 24 hours after preparation Color strength L HH Floatation in drawdown films 4 1 Pigments separation in glass cylinders after 48 3 1 hours of paint storage

[0102] Color strength is a relative scoring is given to compare the two samples. H means higher, L means lower and E means equal tinting strength.

[0103] Rubbing of drawdown films are done and then floatation is judged by giving a core from 1 to 4 where 1 is no floatation and 4 is strong floatation.

[0104] As for pigments separation, paint is placed in a glass cylinders and left for 48 hours and then signs of pigments separation are evaluated and score from 1 to 4 are given where 1 is no separation and 4 is strong separation.

[0105] While illustrative and presently preferred embodiments of the invention have been described in detail hereinabove, it is to be understood that the inventive concepts may be otherwise variously embodied and employed and that the appended claims are intended to be construed to include such variations except insofar as limited by the prior art.